CN109713251B - Lithium ion battery anode material and preparation method and application thereof - Google Patents
Lithium ion battery anode material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a lithium ion battery anode material and a preparation method and application thereof, wherein the anode material contains elements shown in a chemical formula I, is doped with M elements and is coated with N elements; the first chemical formula is as follows: lixNiaCobRcO2Wherein, x is more than 0.95 and less than 1.15, a is more than 0.69 and less than 0.85, b is more than 0 and less than 0.2, c is more than 0.2, a + b + c is more than 0.98 and less than or equal to 1.00, R is selected from manganese or aluminum element, M element is selected from one or more than two of cobalt, zirconium or yttrium, N element is selected from one or more than two of cobalt, zirconium or titanium, wherein, the nickel element accounts for more than 30 percent of the mass fraction of the anode material, preferably more than 40 percent. The anode material has smaller specific surface area, and can effectively improve the high-temperature storage performance of the high-nickel lithium ion secondary battery and the gas expansion performance under the working condition.
Description
Technical Field
The invention relates to the field of lithium ion batteries, mainly relates to the field of lithium ion battery anode materials, and particularly relates to a lithium ion battery anode material and a preparation method and application thereof.
Background
Lithium ion secondary batteries, because of their high energy density, high operating voltage, long cycle life, and the like, have been widely used as power sources for various mobile devices, as energy storage power stations, and even as a gradual replacement for other conventional chemical batteries in the fields of aviation, aerospace, navigation, automobiles, medical devices, and the like.
With the rise of smart phones, smart cars and new energy cars in recent years, the requirements on the energy density and safety of mobile equipment are higher and higher, and currently, common positive electrode materials of lithium ion batteries mainly include lithium cobaltate, lithium manganate, lithium nickel cobalt manganese and lithium iron phosphate. Although lithium cobaltate has high energy density, lithium manganate and lithium iron phosphate materials have low energy density and tend to be gradually replaced by lithium nickel cobalt manganate and high nickel materials with low cobalt content because the storage capacity of cobalt is limited, nickel cobalt manganese materials (ternary materials for short) are usually layered rock salt structure materials, wherein Ni, Co and Mn are adjacent elements in the same period, and materials with the nickel molar content of more than 0.5 in the structural formula are usually called high nickel ternary positive electrode materials.
Research shows that the specific capacity of the nickel cobalt lithium manganate material is increased along with the increase of nickel content, but the apparent performance of the material, such as specific surface area, is unstable, so that the storage performance of the prepared lithium ion battery is extremely unstable, and although the lithium ion battery prepared from the high-nickel material can only be applied to a steel shell battery at present due to large gas production in the use process, the capacity loss and the capacity recovery rate of the battery are obviously weakened after high-temperature storage. The reason is related to the matching of the electrolyte and the stability of production conditions, and the like, and researches show that the specific surface area of the high-nickel material has great influence on the storage performance of the prepared lithium ion battery. In a lithium ion chemical power system, energy output is usually realized by lithium ion transfer, which involves electron transfer between various solid/liquid porous media such as a positive electrode, a negative electrode, a separation membrane, an electrolyte and the like (electrochemical impedance spectroscopy of a lithium ion battery, modesty, gentle wintering, cud clouds, treble, bright, sungey, chemical evolution 2010.22(6) P1044-1057), lithium is inserted into/extracted from the surface of a material in both charging and discharging, when the specific surface area of the material is larger, ion channels of the material are increased on the whole, which is beneficial to the rate capability of the material, but the larger specific surface area also means that more surface defect sites of the material are exposed to the organic electrolyte; research also shows that structural metal elements such as nickel/cobalt/manganese and the like of the positive electrode material, particularly the high-nickel ternary positive electrode material, are dissolved out and transferred into the negative electrode sheet material in the circulation process, and the content of the nickel/cobalt/manganese elements of the negative electrode is gradually increased along with the circulation process, so that the electrochemical performance of the negative electrode material is weakened, which just corresponds to the capacity attenuation of the lithium battery, and therefore, people can easily think that the electrochemical performance of the material can be possibly stabilized if the dissolution of the nickel/cobalt/manganese of the high-nickel ternary material can be controlled.
Regarding how to control the elution of the structural metal, various research institutes have made considerable studies on the elution mechanism, inhibition of elution, and the like. For example, the material is doped to enhance the structural stability, the high-nickel ternary cathode material is coated to improve the compatibility of the material and the electrolyte, the particle morphology is prepared into a structure with higher sphericity, and a film-forming additive is added into the electrolyte to passivate the surface of the material particle, and the like.
Many published patents/documents have proposed the preparation method and application of high nickel ternary cathode materials.
Patent application No. CN201280070138.8 discloses a nickel composite hydroxide and a method for producing the same, a method for producing a non-aqueous electrolyte positive electrode active material, and a lithium ion secondary battery, and a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery, the hexagonal crystal positive electrode active material having a general formula of Li(1+u)NixCoyAlzMntMsO2The expression "u" is 0.05. ltoreq.0.20, x + y + z + t + s "is 1, y 0. ltoreq.0.3, z 0 < 0.1, t 0.001 < 0.05, s 0. ltoreq.0.05, and M is an additive element selected from at least one of the group consisting of Mg, Ca, Ti, V, Cr, Zr, Nb, Mo, and W, and is composed of a plurality of primary particles aggregated to form a substantially spherical secondary particle, and the production process includes: a heat treatment step of heat-treating the nickel-cobalt-aluminum composite hydroxide at a temperature of 105 to 750 ℃; a mixing step of mixing the lithium source and the metal atoms in a ratio of 1: 0.95-1.2 to the number of lithium atoms to form a lithium mixture; and a firing step of forming the mixture in the mixing step in an oxidizing atmosphere at a temperature of 700 to 800 DEG CThe above lithium mixture is fired. The process is that the hydroxide of the precursor is firstly decomposed into oxide, and then the oxide is mixed with lithium salt for reaction to generate the product. However, this method causes instability in the valence of nickel in the reactant due to the presence of moisture during decomposition.
The patent with the application number of CN200810052730.0 discloses a preparation method of spherical aluminum-doped lithium nickel cobalt oxide for a lithium ion battery. Mixing the precursor spherical nickel cobalt aluminum hydroxide with a lithium source (one or a mixture of several of battery-grade lithium hydroxide, lithium nitrate and lithium carbonate). Roasting at 700-800 ℃ for 20-24 hours. And cooling, crushing and grading after roasting to obtain the spherical aluminum-doped lithium nickel cobalt oxide. The process directly mixes the precursor hydroxide and the lithium salt to generate a product in one step, and considers that the removal of moisture influences the preparation of the material, the content of lithium source volatile matters (moisture) is high, the equipment is easy to be seriously corroded at high temperature, and a lot of lithium sources are taken away while the moisture is volatilized, so that the process is not suitable for industrial production in practice.
The patent with the application number of CN201610650420.3 discloses a nickel-cobalt-aluminum ternary precursor, a preparation method thereof, a prepared anode material and a preparation method thereof. Uniformly mixing the obtained nickel-cobalt-aluminum ternary precursor with lithium hydroxide according to a certain proportion (the molar ratio of Li/(Ni + Co + Al) is 0.9-1.2: 1) by adopting a high-speed mixer, heating to 600-800 ℃ at the speed of 2-10 ℃/min in a cover type roasting furnace, preserving heat for 5-20 h, introducing oxygen into the cover type roasting furnace to ensure that the oxygen content in the furnace is more than 70%, naturally cooling to room temperature after heat preservation is finished, crushing and sieving the blank obtained by roasting to obtain the nickel-cobalt-aluminum ternary cathode material.
Disclosure of Invention
The technical problem solved by the invention is as follows: the lithium ion battery prepared by the high-nickel ternary cathode material at present has unstable storage consistency, and the high-nickel lithium ion battery has the problem of performance weakening in a use state, particularly a high-temperature storage state, so that the application of the high-nickel lithium ion battery is limited, and the high-nickel lithium ion battery cannot be applied to a flexible package lithium ion battery at present.
The invention aims to: the high-nickel ternary cathode material with the low specific surface area is developed, and the structural defects on the surface of the high-nickel ternary cathode material are reduced, so that the high-temperature storage performance of the nickel lithium ion battery is improved.
The invention develops the high-nickel ternary cathode material by reducing the specific surface area of the high-nickel ternary cathode material, and the material has less defect sites exposed on the surface of the material due to smaller specific surface area, thereby being beneficial to solving the technical problems.
Meanwhile, the invention also provides the application of the product in a lithium ion battery, and provides a better electrochemical system for a high-energy lithium ion power battery. The application prospect of the high nickel ternary material is expanded.
Specifically, aiming at the defects of the prior art, the invention provides the following technical scheme:
the lithium ion battery anode material is characterized by comprising elements shown in a chemical formula I, M elements and N elements, wherein the M elements are doped in the elements; the first chemical formula is as follows: lixNiaCobRcO2Wherein, x is more than 0.95 and less than 1.15, a is more than 0.69 and less than 0.85, b is more than 0 and less than 0.2, c is more than 0.2, a + b + c is more than 0.98 and less than or equal to 1.00, R is selected from manganese or aluminum element, M element is selected from one or more than two of cobalt, zirconium or yttrium, N element is selected from one or more than two of cobalt, zirconium or titanium, wherein, the nickel element accounts for more than 30 percent of the mass fraction of the anode material, preferably more than 40 percent.
Preferably, in the positive electrode material, the chemical composition formula of the positive electrode material is LixNiaCobRcMdNeO2Wherein 0 < d < 0.1, preferably 0 < d < 0.01, more preferably 0 < d < 0.05, 0 < e < 0.1, preferably 0 < e < 0.08, more preferably 0 < e < 0.05.
Preferably, in the positive electrode material, the mass of the M element accounts for 200-5000ppm, preferably 500-5000ppm of the positive electrode material; the mass of the N element accounts for 200-3000ppm of the positive electrode material, preferably 500-3000 ppm.
Preferably, in the above cathode material, the cathode material includes spherical or spheroidal primary particles or secondary particles formed by agglomeration of the primary particles under a scanning electron microscope.
Preferably, in the positive electrode material, the M element includes zirconium or yttrium.
Preferably, in the positive electrode material, the N element includes titanium or zirconium.
Preferably, in the positive electrode material, the specific surface area of the positive electrode material is 0.3 to 0.6m2(ii) in terms of/g. Median volume particle diameter Dv50Is 2-15 μm.
The invention also provides a preparation method of the cathode material, which is characterized by comprising the following steps:
(1) mixing raw materials including a lithium source, a precursor containing nickel, cobalt and an R element and an M element source, and performing primary sintering at 900 ℃ in an oxygen atmosphere with an oxygen flow of 150-200Nm3/h；
(2) Mixing the product obtained in the step (1) with the material of the N element source, and then carrying out secondary sintering at the temperature of 1000 ℃ in an oxygen atmosphere with the oxygen flow rate of 300-500Nm3And h, obtaining the cathode material.
Preferably, in the above preparation method, the lithium source is selected from lithium carbonate, lithium oxalate or lithium hydroxide monohydrate.
Preferably, in the above production method, the M element source includes an oxide or a salt containing the M element, and preferably, the oxide has a median volume particle diameter Dv5010-500nm, median volume particle diameter D of said saltsv50Is 0.1-100 μm.
Preferably, in the above production method, the N element source includes an oxide or a salt containing an N element, and preferably, the oxide has a median volume particle diameter Dv50100-300nm, the median volume particle diameter D of the saltv50Is 1-50 μm.
Preferably, in the above preparation method, the median volume particle diameter D of the precursorv50Is 5-15 μm.
Preferably, in the above preparation method, the amount of the lithium source added is 40 to 60% by mass of the precursor.
Preferably, in the above preparation method, the addition amount of the M element source accounts for 0.05-1.0% of the mass of the precursor, and the addition amount of the N element source accounts for 0.05-2.0% of the mass of the precursor.
Preferably, in the preparation method, the loss on ignition of the product obtained after the first calcination is 20-40%, preferably 25-35%; the loss on ignition of the product obtained after the second calcination is from 0.1 to 2%, preferably from 0.1 to 1.5%.
Preferably, in the preparation method, the time for the first calcination is 5-15h, and the time for the second calcination is 5-15 h.
The invention also provides a lithium ion battery anode material which is characterized by being prepared by the preparation method.
The invention also provides a lithium ion battery which is characterized by comprising the cathode material.
The invention also provides application of the cathode material or the lithium ion battery in the fields of mobile digital products (3C), electric vehicles (xEV) or energy storage (ESS).
The invention has the beneficial effects that: the specific surface area of the material is reduced through a sintering process and a doping/cladding process, so that the high-temperature storage performance of the high-nickel ternary cathode material is improved. The lithium ion secondary battery prepared by the invention has the characteristics of excellent processing performance, small contact area between the surface of the material and an electrolyte and less side reaction, can improve the storage performance of the lithium battery in a long-term charge state and the gas expansion performance under the working condition, and is suitable for the application fields of xEV, energy storage power station ESS and the like.
Drawings
Fig. 1-a, 1-b, 1-c, and 1-d are electron microscope images of the positive electrode materials described in example 1, comparative example 1, example 3, and comparative example 3, respectively, at a magnification of 5000.
FIG. 2 is a graph of the cycle capacity retention ratio of 0.5C/0.5C at 45 ℃ of lithium ion batteries prepared from the positive electrode materials described in examples 1, 3, 7, 1, 3 and 5.
Fig. 3-a is a graph showing a voltage and temperature rise curve of a needle punching test of lithium ion batteries prepared from the cathode materials described in example 1 and comparative example 1.
Fig. 3 b is a graph showing a voltage and temperature rise curve of a needle punching test of lithium ion batteries prepared from the cathode materials described in example 4 and comparative example 4.
Detailed Description
In view of the fact that the high-temperature storage performance of the lithium ion battery needs to be improved at present, the invention provides a high-temperature storage improved high-nickel ternary cathode material, and a preparation method and application thereof.
In a preferred embodiment, the positive electrode material of the present invention is characterized in that: the specific surface area of the material is reduced during sintering of the material.
Preferably, the specific surface area of the positive electrode material is 0.3 to 0.6m2/g。
Preferably, the positive electrode material has a secondary sphere structure or a secondary particle agglomerate structure.
Preferably, the positive electrode material has a structural formula of LixNiaCobMncMdNeO2Wherein, the molar content of x is more than 0.95 and less than 1.15, a is more than 0.69 and less than 0.85, b is more than 0 and less than 0.2, c is more than 0 and less than 0.2, a + b + c is more than or equal to 0.98 and less than or equal to 1.00, d is more than or equal to 0 and less than 0.1, and the manganese (Mn) element can be replaced by aluminum (Al) element, is doped with M element and is coated with N element; the M element is selected from one or more than two of cobalt, zirconium or yttrium, and the N element is selected from one or more than two of cobalt, zirconium or titanium.
The preparation method of the cathode material comprises the following steps:
(1) mixing raw materials comprising a lithium source, a nickel-cobalt-manganese precursor and an M element source, and sintering at 400-900 ℃;
(2) mixing the product obtained in the step (1) with a material of an N element source to obtain a pre-coated object;
(3) and carrying out secondary sintering on the pre-coating at the temperature of 700-1000 ℃ to obtain the cathode material.
Preferably, in the above preparation method, the sintering of the ternary cathode material is performed in an oxygen atmosphere, and the volume content of oxygen is 40-98%.
Preferably, in the above preparation method, the material sintering is performed in an oxygen atmosphere, and the amount of oxygen is 150-3/h。
Preferably, the median particle diameter D of the positive electrode material isv50＝2-15μm。
Preferably, in the positive electrode material, the M element includes zirconium or yttrium, and the N element includes titanium or zirconium.
Preferably, the invention also provides a lithium ion battery cathode material prepared by the preparation method.
Preferably, the present invention also provides a lithium ion battery comprising the above-mentioned positive electrode material.
The cathode material or the lithium ion battery can be directly applied to the fields of mobile digital products (3C), electric vehicles (xEV) or energy storage (ESS).
In the present invention, the "lithium ion battery" refers to: a secondary battery (rechargeable battery) operates by mainly relying on lithium ions moving between a positive electrode and a negative electrode. The "lithium ion battery positive electrode material" refers to: an active material for a positive electrode of a lithium ion battery.
The "doping" refers to: in order to improve the properties of certain materials, other elements or compounds are purposefully incorporated into such materials.
The term "coating" refers to: the surface of the particle is treated by a physical or chemical method according to needs, a coating layer is introduced on the surface of the particle, and the coated particle can be regarded as composite powder consisting of a core layer and a shell layer.
The "lithium source" refers to: the raw material contains lithium element.
The "nickel-cobalt-manganese precursor" refers to: the ternary cathode material precursor is prepared by taking nickel salt, cobalt salt and manganese salt as raw materials, and the commonly used nickel-cobalt-manganese precursor is nickel-cobalt-manganese hydroxide or oxide.
The "M element source" refers to: the raw material contains M element.
The "N element source" refers to: the raw material contains N element.
The "sintering" refers to: through heat treatment, the powder or pressed compact is converted into compact/crystal.
In another preferred embodiment, the method for preparing the preferred high-nickel ternary cathode material of the present invention comprises the following steps:
a) mixing (physical dispersion), namely preparing fluffy powdery materials or partially slightly caking materials from lithium salts, precursors of high-nickel ternary materials, target doping element raw materials and the like by adopting a wet method, a dry method or a quasi-dry method. The lithium salt is selected from lithium carbonate, lithium hydroxide monohydrate, lithium acetate and/or lithium oxalate.
b) Cooling the material obtained by the first sintering at high temperature, and introducing the cooled material into a crusher for further dispersion and crushing to form powdery material with uniform components.
c) Mixing the materials. And c) adding the powdery material obtained in the step b) into a stirring device again for stirring, adding a small amount of auxiliary agent capable of reducing the surface area, uniformly mixing, and adding or not adding the solvent according to the situation.
d) Sintering. Sintering the powdery material obtained in the step c) in oxygen-enriched air at the temperature of more than 500 ℃, and then carrying out protective atmosphere (N)2) And (5) naturally cooling. The sintering equipment refers to equipment such as a roller kiln, a ventilation atmosphere kiln and the like.
e) And d, crushing the material obtained in the step d) for the second time to prepare the high-nickel ternary cathode material with the target product and low specific surface area. The crushing equipment refers to cyclone vortex crusher, air flow crusher and other equipment.
The following examples further illustrate the positive electrode material of the present invention, its preparation and use.
The information on each reagent and apparatus used in the following examples is shown in tables 1 and 2.
TABLE 1 list of reagent information used in the examples
Example 1
Mixing materials: selecting 200L plow mixer, starting stirring (rotating speed 25rpm), and adding 100kg of Ni-Co-Mn precursor (Ni) under stirring0.61Co0.19Mn0.20(OH)2(particle size D)v507 μm, effective component content 98.5%), and then 46.1kg of lithium hydroxide monohydrate powder (granularity D) is weighed according to the Li/(Ni + Co + Mn) molar ratio of 1.01v5025 mu m and 99.5 percent of effective substance) into a mixer, adding 37.0kg of deionized water according to the solid content of 80 percent by weight under the stirring condition, then adding 0.57kg of basic cobalt carbonate (the cobalt content added according to the finished product accounts for 3000ppm of the mass of the anode material), stirring for 2h, further reducing the speed (5rpm), stirring for 6h, discharging and forming a paste material with certain forming degree for sealing and standby.
Primary sintering: a24 m ventilated roller kiln is adopted. Setting the temperature of the heating zone at 400 ℃, and introducing oxygen-enriched air (the integral number of oxygen in the oxygen-enriched air is 45%, and the flow rate is 400 Nm)3H) filling the materials into a ceramic bowl for the 1 st sintering, wherein the sintering time is 10 h. The materials are cooled to normal temperature under the protection of dry nitrogen, the weight of the materials in and out is weighed, and the loss on ignition is 34.7 percent calculated by the raw materials.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear velocity of a grading wheel is 25m/s) to obtain a 1 st sintered semi-finished product.
And adding the obtained 1 st sintering semi-finished powder material into a 200L plow mixer again, starting stirring (the main rotating speed is 90rpm, the side cutter speed is 1300rpm), adding a solution in which 1.17kg of zirconium nitrate pentahydrate (the added zirconium accounts for 3000ppm of the mass of the anode material) is dissolved by 0.5kg of deionized water, uniformly mixing and discharging.
And (3) secondary sintering: a24 m ventilated roller kiln is adopted. Setting the temperature of the heating zone to 1000 ℃, and introducing oxygen-enriched air (the volume fraction of oxygen in the oxygen-enriched air is 98%, and the flow rate is 300 Nm)3And h) putting the materials into a ceramic bowl for 2-time sintering, wherein the sintering time is 10 h. The materials are cooled to normal temperature under the protection of dry nitrogen, the weight of the materials in and out is weighed, and the loss on ignition is 1.2 percent calculated by the raw materials.
Crushing: then crushing by using a vortex flow crusher (the linear speed of a grading wheel is 65m/s) to obtain the nickel cobalt lithium manganate cathode material.
The chemical formula of the anode material of the invention is Li by adopting dilute hydrochloric acid digestion and ICP detection and accounting1.01Ni0.61Co0.1 9Mn0.20Zr0.003O2M element is cobalt, D is 0.005, N element is zirconium, e is 0.003, and the median volume particle diameter D of the positive electrode material is detected by a Malvern particle sizerv50It was 7.3 μm.
Example 2
Mixing materials: a200-liter Y-shaped mixer is selected. The stirring was started (50 rpm) and 100kg of nickel-cobalt-manganese precursor (Ni) was added with stirring0.61Co0.20Mn0.20(OH)2(particle size D)v507 μm, effective component content 98.8%), and 41.5kg of lithium carbonate powder (particle size D) were weighed in a molar ratio of Li/(Ni + Co + Mn) of 1.04v505 μm, content of active substance 99.8%) was added to a mixer, and 20.0kg of deionized water and 0.054kg of yttrium oxide (ceramic grade, particle size D) were added at 90% solids content with stirringv500.3 mu m, the purity is 99.0 percent, the content of yttrium is 450ppm of the anode material based on the finished product), stirring for 2 hours, then further reducing the speed (3-5rpm), stirring for 1 hour, discharging, forming a paste material with a certain forming degree, discharging, and sealing for later use.
Primary sintering: the primary sintering was carried out in a similar manner to example 1, using oxygen-enriched airThe integral number of the ferrite is 40 percent, and the flow rate is 400Nm3The sintering temperature is 900 ℃, the sintering time is 5h, and the loss on ignition of the raw material in the example 2 is 33.8 percent.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
The obtained 1 st sintering semi-finished powder material is added into a 200L Y-shaped mixer again, stirring is started (rotating speed: 60rpm), 7.45kg of tetrabutyl titanate (industrial grade, the content of effective components is 20 percent, and the content of titanium accounts for 2000ppm of the anode material in terms of finished products) is added, and the materials are uniformly mixed and discharged.
And (3) secondary sintering: the second sintering was carried out in a similar manner to example 1, with the volume fraction of oxygen in the oxygen-enriched air being 98% and the flow rate being 500Nm3The sintering temperature is 700 ℃, the sintering time is 12h, and the loss on ignition of the semi-finished product in example 2 is 0.4 percent based on the raw material of the semi-finished product.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium manganate positive electrode material.
The chemical formula of the anode material of the invention is Li by adopting dilute hydrochloric acid digestion and ICP detection and accounting1.04Ni0.61Co0.2 0Mn0.20Y0.0004Ti0.004O2M element is yttrium, D is 0.0004, N element is titanium, e is 0.004, and the median volume particle diameter D of the positive electrode material is detected by a Malvern particle sizerv50And 3.8 μm.
Example 3
Mixing materials: A200L fusion machine is selected. Starting stirring (rotating speed 600rpm), and adding 100kg of nickel-cobalt-manganese precursor (Ni) under stirring0.70Co0.15Mn0.15(OH)2(particle size D)v5012 μm, effective component content 98.5%), and 58.6kg of lithium oxalate powder (granularity D) were weighed according to the molar ratio of Li/(Ni + Co + Mn) being 1.06v504.5 μm, 99.5% active substance) was added to a fusion machine, 10kg of deionized water and 0.51kg of yttrium oxide (ceramic grade, particle size D) were addedv500.3 μm, 99.0% purity, and the yttrium content is 4000ppm of the positive electrode material in terms of finished product), stirringStirring for 2h, further reducing the speed (500rpm), stirring for 20min, discharging and sealing for later use.
Primary sintering: the same procedure as in example 1 was used to carry out the primary sintering at an oxygen content of 50% by volume and a flow rate of 400Nm3The sintering temperature is 450 ℃, the sintering time is 15h, and the loss on ignition of the raw material in the example 3 is 33.6 percent.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
And adding the obtained 1 st sintered semi-finished powdery material into a 200L fusion machine again, starting stirring (rotating speed of 2000rpm), adding 0.3kg of deionized water and 0.12kg of zirconium nitrate pentahydrate (industrial grade, purity is 97.0%, and zirconium content is 300ppm of the anode material in terms of finished product), uniformly mixing and discharging.
And (3) secondary sintering: the second sintering was carried out in the same manner as in example 1 except that the volume fraction of oxygen in the oxygen-enriched air was 98% and the flow rate was 400Nm3The sintering temperature is 920 ℃, the sintering time is 5h, and the loss on ignition of the semi-finished product in example 3 is 0.5 percent based on the raw material of the semi-finished product.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium manganate positive electrode material.
The anode material of the invention with the chemical formula of Li is obtained by adopting dilute hydrochloric acid for digestion and ICP detection and accounting1.06Ni0.70Co0.1 5Mn0.15Y0.004Zr0.0003O2M element is yttrium, D is 0.004, N element is zirconium, e is 0.0003, and the median volume particle diameter D of the positive electrode material is detected by a Malvern particle sizerv50It was 15.5 μm.
Example 4
Mixing materials: A400L kneader is selected. The stirring was started (40 rpm), and 100kg of nickel-cobalt-manganese precursor (Ni) was added with stirring0.79Co0.08Mn0.11(OH)2(particle size D)v5010 μm, effective component content 98.7%), and 48.4kg of lithium hydroxide monohydrate powder (particle size D) was weighed according to the Li/(Ni + Co + Al) molar ratio of 1.05v5015 μm, effective component content99.8 percent), adding 33kg of deionized water and 0.125kg of tetrahydrate yttrium acetate (chemical purity, purity is 95.5 percent, and the content of yttrium is 300ppm of the anode material in terms of finished product) into a kneader, stirring for 1 hour, then further reducing the speed (20rpm), stirring for 20min, discharging and sealing for later use.
Primary sintering: the same method as that of example 1 was adopted to carry out primary sintering, the sintering temperature was 600 ℃, the sintering time was 10 hours, and the loss on ignition of example 4 was 29.3% based on the raw materials.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
And adding the obtained 1 st sintering semi-finished product powdery material into a 400L kneader again, starting stirring (rotating speed 50rpm), adding 3.7kg of deionized water and 0.096kg of cobalt acetate (chemical purity, purity 99.5%, cobalt content is 300ppm of the anode material in terms of finished product), uniformly mixing and discharging.
And (3) secondary sintering: the second sintering was carried out in the same manner as in example 1, except that the sintering temperature was 930 ℃ and the sintering time was 7 hours, and that in example 4, the loss on ignition based on the raw material of the semi-finished product was 0.2%.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium manganate positive electrode material.
The anode material of the invention with the chemical formula of Li is obtained by adopting dilute hydrochloric acid for digestion and ICP detection and accounting1.05Ni0.79Co0.0 8Mn0.11Y0.0003O2M element is yttrium, D is 0.0003, N element is cobalt, e is 0.0005, and the median volume particle diameter D of the positive electrode material is detected by a Malvern particle sizerv50And 12.3 μm.
Example 5
Mixing materials: A400L kneader is selected. Starting stirring (rotating speed 30rpm), and adding 100kg of Ni-Co-Mn precursor Ni under the stirring condition0.80Co0.11Mn0.09(OH)2(particle size D)v508 μm, effective component content 98.8%), and 47.7kg of lithium hydroxide monohydrate powder (particle size D) were weighed in a molar ratio of Li/(Ni + Co + Al) of 1.05v5025 μm, effective component content98.8 percent of the weight of the anode material, 35kg of deionized water and 0.71kg of zirconium oxide (industrial grade, the purity is 95.5 percent, and the content of zirconium is 5000ppm of the anode material based on the finished product) are added into a kneader, stirred for 50min, further stirred at a reduced speed (20rpm) for 20min, discharged and sealed for later use.
Primary sintering: the same method as that of example 1 was adopted to carry out primary sintering, the sintering temperature was 500 ℃, the sintering time was 12 hours, and the loss on ignition of example 5 was 28.9% of the raw materials.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
Adding the obtained 1 st sintering semi-finished powder material into a 400L kneader again, starting stirring (rotating speed 60rpm), adding 37kg deionized water, and adding 0.54kg nano titanium dioxide (D)v50:0.3 μm, industrial grade, 98.0% purity, titanium content is 3000ppm of the anode material in terms of finished product), and the materials are mixed uniformly and discharged.
And (3) secondary sintering: the second sintering was carried out in the same manner as in example 1, except that the sintering temperature was 760 ℃ and the sintering time was 10 hours, and that in example 5, the loss on ignition based on the raw material of the semi-finished product was 0.1%.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium manganate positive electrode material.
The anode material of the invention with the chemical formula of Li is obtained by adopting dilute hydrochloric acid for digestion and ICP detection and accounting1.05Ni0.80Co0.1 1Mn0.09Ti0.007Zr0.006O2M element is zirconium, D is 0.007, N element is titanium, e is 0.006, and the median volume particle diameter D of the positive electrode material is detected by a Malvern particle sizerv50It was 8.3 μm.
Example 6
Mixing materials: A200L plough type mixer is selected. Starting stirring (rotating speed 25rpm), and adding 100kg of nickel-cobalt-manganese precursor (Ni) under stirring0.81Co0.15Al0.05(OH)2Particle size Dv507 μm, effective component content 98.8%), and 42.7kg of carbonic acid is weighed according to the molar ratio of Li/(Ni + Co + Al) being 1.06Lithium powder (particle size D)v503.5 mu m and the content of effective substances is 99.8 percent) is added into a mixer, 20.0kg of deionized water and 1.67kg of tetrahydrate yttrium acetate (industrial grade, the purity is 95.5 percent, and the content of yttrium is 4000ppm of the anode material based on the finished product) are added according to the solid content of 90 percent by weight under the condition of stirring, the speed is further reduced (3-5rpm) after the stirring is carried out for 2 hours, the stirring is carried out for 6 hours, and the paste material with certain forming degree is formed and is sealed for later use.
Primary sintering: the same method as that of example 1 was adopted to carry out primary sintering, the sintering temperature was 570 ℃, the sintering time was 8 hours, and the loss on ignition of example 6 was 26.3% of the raw materials.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
The obtained 1 st sintered semi-finished powdery material was again added to a 200L plow mixer, stirring was started (main rotation speed 120rpm, side cutter rotation speed: 1500rpm), and 0.068kg of cobalt (D) hydroxide was addedv500.3 mu m, industrial grade, 98.0 percent of purity, the cobalt content of which is 400ppm of the anode material in terms of finished product), and 7.5kg of tetrabutyl titanate (the effective component content of which is 20 percent in terms of finished product, the titanium content of which is 2000ppm of the anode material in terms of finished product) are uniformly mixed and discharged.
And (3) secondary sintering: the second sintering was carried out in the same manner as in example 1, except that the sintering temperature was 830 ℃, the sintering time was 8 hours, and the loss on ignition in example 6 was 0.23% based on the raw material of the semi-finished product.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium aluminate cathode material.
The anode material of the invention with the chemical formula of Li is obtained by adopting dilute hydrochloric acid for digestion and ICP detection and accounting1.06Ni0.81Co0.1 5Al0.05Y0.005Ti0.004O2In addition, the cathode material is doped with M element and coated with N element, wherein the M element is yttrium, D is 0.005, the N element is cobalt and titanium, e is 0.011 in total, and the median volume particle diameter D of the cathode material is detected by a Malvern particle sizerv50It was 7.1 μm.
Example 7
Mixing materials: A200L kneader is selected. Starting stirring (rotating speed 30rpm), and adding 100kg of Ni-Co-Al precursor Ni under the stirring condition0.80Co0.15Al0.04(OH)2(particle size D)v508 μm, the content of active substance is 99.0 percent, and 42.7kg of lithium carbonate powder (the granularity D is equal to 1.05) is weighed according to the molar ratio of Li/(Ni + Co + Al)v503.5 mu m, the content of effective substances is 99.8 percent), 31kg of deionized water and 0.75kg of nano zirconium hydroxide (ceramic grade, the purity is 98.0 percent, and the content of zirconium is 4000ppm of the anode material in terms of finished products) are added into a kneader, stirred for 50min, then further stirred at a reduced speed (20rpm) for 20min, discharged and sealed for later use.
Primary sintering: the same method as that of example 1 was adopted to carry out primary sintering, the sintering temperature was 400 ℃, the sintering time was 10 hours, and the loss on ignition of example 7 was 26.3% of the raw materials.
Crushing: and (3) crushing by using a vortex flow crusher (the linear velocity of a grading wheel is 35m/s) to obtain a 1 st sintered semi-finished product.
And adding the obtained 1 st sintering semi-finished product powdery material into a 200L kneader again, starting stirring (rotating speed 50rpm), adding 40kg of deionized water, adding 0.081kg of nano titanium dioxide (Dv 50: 0.3 mu m, industrial grade, purity 98.0 percent, content of titanium calculated as a finished product is 450ppm of the anode material), uniformly mixing and discharging.
And (3) secondary sintering: the second sintering was carried out in the same manner as in example 1, except that the sintering temperature was 840 ℃ and the sintering time was 7 hours, and that in example 7, the loss on ignition based on the raw material of the semi-finished product was 0.27%.
Crushing: and (4) crushing by using a cyclone vortex crusher (the linear speed of a grading wheel is 45m/s) to obtain the doped nickel cobalt lithium aluminate cathode material.
The anode material of the invention with the chemical formula of Li is obtained by adopting dilute hydrochloric acid for digestion and ICP detection and accounting1.05Ni0.80Co0.1 5Al0.04Zr0.004Ti0.001O2In addition, the cathode material is doped with M element and coated with N element, wherein the M element is zirconium, D is 0.004, the N element is titanium, e is 0.001, and the median volume particle diameter D of the cathode material is detected by a Malvern particle sizerv50It was 3.5. mu.m.
Example 8 (comparative example)
The high nickel ternary material was prepared according to the same procedure as example 1 without adding doping elements and coating elements to obtain comparative example 1 for further use.
The high-nickel ternary cathode material was prepared according to the same preparation procedure as example 3 without adding the doping element and the coating element, and comparative example 3 was obtained for future use.
The high-nickel ternary cathode material was prepared according to the same process conditions as in example 4 without adding doping elements and coating elements, and comparative example 4 was obtained for use.
The high-nickel ternary cathode material was prepared according to the same procedure as in example 5 without adding the doping element and the coating element, and comparative example 5 was obtained for further use.
The high nickel ternary positive electrode material was prepared according to the same process conditions as in example 7 without adding the doping element and the coating element, and comparative example 7 was obtained for further use.
Comparative example 8 similar to example 5, except that the nickel-cobalt-manganese precursor used was Ni0.46Co0.08Mn0.46(OH)2(technical grade, content 99 wt%).
Example 9 scanning Electron microscopy testing
The positive electrode materials obtained in example 1, comparative example 1, example 3 and comparative example 3 were subjected to SEM test by scanning electron microscope to obtain the results of fig. 1-a, fig. 1-b, fig. 1-c and fig. 1-d, respectively.
As can be seen from fig. 1-a and 1-b, the positive electrode material has a large difference in morphology, and the particles of example 1 have a uniform morphology and size, wherein the secondary particle size is about 7.3 μm, the primary spherical particles constituting the secondary spherical particles have a uniform size (0.02 to 0.5 μm), the primary particles and the secondary particles of the positive electrode material of comparative example 1 have different sizes, and the primary particles grow disorderly. FIG. 1-d shows the same problem as FIG. 1-c, and the particles have elongated unknown substances on the surface, which may be unreacted lithium oxide and its salt crystals. In the nickel-cobalt-aluminum positive electrode material, the consistency of the size of primary particles of nickel-cobalt-aluminum particles and the performance of the positive electrode material has very important influence, the size of the primary particles is consistent, the specific capacity and the platform of the material are high, the pulping viscosity is stable in the processing process, the gas yield of the prepared lithium battery is low, and the cycle of the battery is good.
Example 10 specific surface area test
The specific surface areas of the solid substances of the cathode materials prepared in the above examples 1-7, comparative example 1, comparative example 3, comparative example 4, comparative example 5, comparative example 7 and comparative example 8 were measured by reference to GB/T19587-.
Table 3 specific surface area test results of examples
As can be seen from Table 3, comparative example 8 has a specific surface area of 0.83m although it is a nickel-cobalt-manganese cathode material having a low nickel content2A/g, although slightly smaller than examples 1 to 7, still greater than 0.6m2In terms of/g, there is a possibility that the produced lithium ion secondary battery may be caused to swell.
As can be seen from Table 3, the specific surface areas of the examples are all 0.6m2The added coating elements can participate in the synthesis reaction on the surface of the material in the post high-temperature treatment process, and simultaneously, the defects on the surface of the material are eliminated by virtue of the high-temperature effect, so that the aims of reducing the defects on the surface of the material and reducing the specific surface area of the material are fulfilled.
Example 11 full cell preparation and Performance evaluation
Positive electrode material powders prepared in examples 1 to 7, and comparative examples 1, 3, 4, 5, 7, and 8 were used as positive electrode active materials, and 21700 cylindrical batteries were prepared as power batteries having a capacity of about 4.86Ah, respectively, for examining high voltage cycle and safety effects. A suitable wound structure 21700 steel can cell was evaluated for a cell diameter of 21mm and a height of about 70mm, and was prepared by a conventional process.
The positive pole piece is prepared by preparing slurry, coating, cold pressing, slitting and the like. The effective positive active material content in the pole piece is 97.5%, and the average pole piece coating weight is 0.0260g/cm3The coating width of the pole piece is 62mm, and the total area of the active substances of the pole piece is 937.4cm2The thickness of the aluminum foil base material is 13 mu m, and the compacted density of the pole piece is 3.2g/cm calculated by active substances3。
The negative pole piece is prepared by the processes of preparing slurry, coating, cold pressing, slitting and the like. When the artificial graphite is used as the negative active material, the content of the prepared pole piece effective negative active material (artificial graphite) is 96.0 percent, and the coating weight of the pole piece is 0.0164g/cm2The coating width of the pole piece is 63.5mm, and the total area of the active substances of the pole piece is 1009.65cm2The thickness of the copper foil base material is 9 mu m, and the compacted density of the pole piece is 1.65g/cm calculated by active substances3。
The anode plate welded with an aluminum tab, an isolation film (a PP/PE/PP composite isolation film with the thickness of 16 mu m and subjected to nano-alumina coating treatment), a cathode plate welded with a nickel tab and the like are sequentially wound to prepare a cylindrical bare cell, the tab is sleeved with an insulating ring and then placed into a shell, the nickel tab is welded at the bottom of a cylinder by laser welding, then the bare cell with a groove is prepared by curling, and cooling and liquid injection are performed after drying. In order to further verify the influence of free lithium on gas production performance, a Vent component which can turn over under certain pressure is welded while a CID and PTC components are welded, after the components are packaged and stood, the components are formed in an LIP-10AHB06 type high-temperature formation machine (formation voltage is 0-4.2V, 0.1C is charged, 0.2C is discharged, temperature is 45 +/-2 ℃), a capacity test is carried out (test voltage is 3.0-4.2V, 0.2C, 0.5C), and cells with qualified quality are selected for subsequent performance evaluation.
The lithium cell prepared in the example was placed in a 45 ℃ oven, and the electrode was put into a high temperature formation machine of LIP-10AHB06 type for 1C/1C, 3.0-4.2V cycle detection, to obtain the 45 ℃ cycle results of FIG. 2. As can be seen from fig. 2, the coating amount of the titanium element corresponding to example 2, example 5, example 6, and example 7 of the present invention is 0.001 or more, and the cycle performance of the lithium ion battery prepared by the method is excellent, which indicates that the improvement effect of the method on the nickel-cobalt-aluminum ternary material is better, the capacity retention rate is still greater than 80% after 300 cycles, which exceeds the expected result, and the capacity retention rates of the lithium ion batteries prepared by examples 1 to 7 after 300 cycles are respectively 86%, 95%, 89%, 88%, 93%, 95%, and 93%. The comparative examples 1, 3, 4, 5, 7 and 8 are respectively 81%, 60%, 68%, 60%, 60% and 72%, and the example 1 is slightly improved compared with the comparative example 1 (81%), and the other comparative examples have the phenomenon of circulating water jump in the later period of circulation, so that the application of the material is limited, and related mechanisms need to be further researched.
EXAMPLE 11 nail penetration test
Nailing (nail diameter phi 8mm, piercing speed 20-25 mm/s) the 21700 type cylindrical lithium ion secondary battery prepared by the positive electrode material prepared by the embodiment 1-7, the embodiment 1, the embodiment 3 and the embodiment 4 according to QC/T743-, the cells were then left to stand for 2 hours for standard testing, with representative results as shown in fig. 3-a, fig. 3-b, and table 4.
TABLE 4 results of nail penetration test in examples
As shown in fig. 3-a, the lithium batteries prepared in example 1 and comparative example 1 of the present invention can pass through the nail prick abuse condition, and the temperature rise is not obvious, but the lithium batteries prepared in comparative example 1 have extremely unstable temperature and voltage during testing, and the curves are in a fluctuation state, which indicates that some protection structures may play roles during the testing process. Meanwhile, as shown in table 4, the temperature rise of the lithium ion battery cells prepared in examples 1 to 7 is within 120 ℃, which is lower than the closed pore temperature of the isolating film, and the battery cells can still detect the internal resistance after being nailed. As can be seen from FIG. 3-b, the temperature rise of the cell of comparative example 4 is more obvious than that of example 4 (120 ℃), the internal resistance in the later period can not be detected, the temperature rise of the cell of comparative example 4 is detected to be 500 margins, the cell is actually ignited and burned, and the temperature of the core body is far higher than the upper limit (500 ℃) of the temperature which can be detected by the K-type thermocouple. The invention can obviously improve the safety performance of the high-nickel ternary cathode material after the cathode material is processed, thereby achieving the aim of development.
Example 12 overcharge test
The 21700 type cylindrical lithium ion secondary battery prepared by the positive electrode material prepared in the embodiment 1, the embodiment 4, the embodiment 5, the comparative example 1, the comparative example 4 and the comparative example 5 is welded with a lead-out tab and then connected to a channel of a battery overcharge and overdischarge testing machine, the battery is firstly discharged to 3.0V at a current of 1C (4.86A), a thermocouple is connected and placed in a fume hood, and the battery is charged by a constant-current and constant-voltage power supply, wherein the current is 3C, the voltage is 4.6V, and the cell voltage is 4.6V. The cell temperature change was monitored during the test and the test was terminated when the cell temperature dropped to about 10 c below the peak value.
Table 5 example overcharge test results
As can be seen from table 5 above, the security of the 21700 type electrical core prepared after treatment is significantly improved, all examples pass the 4.6V overcharge test, and the comparative example electrical core begins to leak/catch fire before the test time is completed, indicating that the reduction of the specific surface area by the doping coating technology has a greater improvement on the security of the lithium ion battery prepared from the high nickel material.
While specific embodiments of the invention have been described with reference to the above examples, it will be understood by those skilled in the art that the foregoing examples are for purposes of illustration only and are not intended to limit the scope of the invention, which is to be construed as limiting the present invention.
Claims (23)
1. The lithium ion battery anode material is characterized by comprising elements shown in a chemical formula I, M elements and N elements, wherein the M elements are doped in the elements; the first chemical formula is as follows: lixNiaCobRcO2Wherein x is more than 0.95 and less than 1.15, a is more than or equal to 0.8 and less than 0.85, b is more than 0 and less than 0.2, c is more than 0.2, a + b + c is more than or equal to 0.98 and less than or equal to 1.00, R is selected from manganese or aluminum elements, M elements comprise yttrium, and N elements comprise zirconium or titanium;
the chemical composition formula of the cathode material is LixNiaCobRcMdNeO2Wherein d is more than 0 and less than 0.1, e is more than 0 and less than 0.1, the mass fraction of nickel element in the anode material is more than 40 percent, and the specific surface area of the anode material is 0.34-0.45m2/g；
The preparation method of the lithium ion battery anode material comprises the following steps:
(1) mixing raw materials including a lithium source, a precursor containing nickel, cobalt and an R element and an M element source, and performing primary sintering at 900 ℃ in an oxygen atmosphere with an oxygen flow of 150-200Nm3/h；
(2) Mixing the product obtained in the step (1) with the material of the N element source, and then carrying out secondary sintering at the temperature of 1000 ℃ in an oxygen atmosphere with the oxygen flow rate of 300-500Nm3Obtaining the cathode material;
wherein the addition amount of the M element source accounts for 0.05-1% of the mass of the precursor, and the addition amount of the N element source accounts for 0.05-2% of the mass of the precursor.
2. The positive electrode material according to claim 1, wherein 0 < d < 0.05.
3. The positive electrode material according to claim 1, wherein 0 < d.ltoreq.0.01.
4. The positive electrode material according to claim 1, wherein 0 < e.ltoreq.0.08.
5. The positive electrode material according to claim 2, wherein 0 < e.ltoreq.0.08.
6. The positive electrode material according to claim 3, wherein 0 < e.ltoreq.0.08.
7. The positive electrode material according to claim 4, wherein 0 < e.ltoreq.0.05.
8. The positive electrode material as claimed in any one of claims 1 to 7, wherein the M element accounts for 200-5000ppm of the positive electrode material, and the N element accounts for 200-3000ppm of the positive electrode material.
9. The positive electrode material according to any one of claims 1 to 7, wherein the positive electrode material comprises primary particle bodies or secondary particle bodies formed by agglomeration of the primary particle bodies, the morphology of which is spherical or spheroidal, under a scanning electron microscope.
10. A method for producing a positive electrode material according to any one of claims 1 to 9, characterized by comprising the steps of:
(1) mixing raw materials comprising a lithium source, a precursor containing nickel, cobalt and an R element and an M element source, carrying out primary sintering at the temperature of 900 ℃ in an oxygen atmosphere,the oxygen flow rate of the oxygen atmosphere is 150-200Nm3/h；
(2) Mixing the product obtained in the step (1) with the material of the N element source, and then carrying out secondary sintering at the temperature of 1000 ℃ in an oxygen atmosphere with the oxygen flow rate of 300-500Nm3And h, obtaining the cathode material.
11. The production method according to claim 10, wherein the lithium source is selected from lithium carbonate, lithium oxalate or lithium hydroxide monohydrate.
12. The production method according to claim 10, wherein the M element source includes an oxide or a salt containing an M element.
13. The production method according to claim 12, wherein the median volume particle diameter D of the oxide containing the M elementv5010-500nm, and the median volume particle diameter D of the salt containing M elementv50Is 0.1-100 μm.
14. The production method according to claim 11, wherein the M element source includes an oxide or a salt containing the M element.
15. The production method according to claim 14, wherein the median volume particle diameter D of the oxide containing the M elementv5010-500nm, and the median volume particle diameter D of the salt containing M elementv50Is 0.1-100 μm.
16. The production method according to any one of claims 10 to 15, wherein the N element source includes an oxide or a salt containing N element.
17. The production method according to claim 16, wherein the oxide containing an N element has a median volume particle diameter Dv50100-300nm, and the median volume particle diameter D of the salt containing the N elementv50Is 1-50 μm.
18. The preparation method according to any one of claims 10 to 15, wherein the lithium source is added in an amount of 40 to 60% by mass of the precursor.
19. The preparation method according to claim 16, wherein the lithium source is added in an amount of 40-60% by mass of the precursor.
20. The preparation method according to claim 17, wherein the lithium source is added in an amount of 40-60% by mass of the precursor.
21. A positive electrode material for a lithium ion battery, characterized in that the positive electrode material is prepared by the preparation method of any one of claims 11 to 20.
22. A lithium ion battery comprising the positive electrode material according to any one of claims 1 to 9 and 21.
23. Use of the positive electrode material according to any of claims 1-9 and 21, or the lithium ion battery according to claim 22 in the field of mobile digital products, electric vehicles or energy storage.
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